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Title: Synthesis and Characterization of Potassium Aryl- and Alkyl-Substituted Silylchalcogenolate Salts

Treatment of either triphenyl(chloro)silane or tert-butyldiphenyl(chloro)silane with potassium metal in THF, followed by addition of 18-crown-6, affords [K(18-crown-6)][SiPh 3] (1) and [K(18-crown-6)][SiPh 2 tBu] (2), respectively, as the reaction products in high yield. Compounds 1 and 2 were fully characterized including by multi-nuclear NMR and IR spectroscopies. Addition of elemental chalcogen to either 1 or 2, results in facile chalcogen insertion into the potassium-silicon bond to afford the silylchalcogenolates, [K(18-crown-6)][E– SiPh2R] (E = S, R = Ph (3); Se, R = Ph (4); E = Te, R = Ph (5); E = S, R = tBu (6); E = Se, R = tBu (7); E = Te, R = tBu (8)), in moderate to good yield. The silylchalcogenolates reported herein were characterized by multi-nuclear NMR and IR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the reported compounds crystallize as discrete monomers in the solid-state, a structural feature not previously observed in silylchalcogenolates, providing well-defined access routes into systematic metal complexation studies.
Authors:
 [1] ;  [2] ;  [2] ;  [3] ;  [3] ;  [3]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Transylvania Univ., Lexington, KY (United States)
  2. Transylvania Univ., Lexington, KY (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Report Number(s):
LA-UR-15-28775
Journal ID: ISSN 1477-9226
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 45; Journal Issue: 24; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry
OSTI Identifier:
1335624